CN111276598A - Printed bismuth telluride film suitable for wide temperature range and preparation method thereof - Google Patents
Printed bismuth telluride film suitable for wide temperature range and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a printed bismuth telluride film suitable for a wide temperature range and a preparation method thereof. The point defects in the film can be effectively controlled by using the bismuth telluride film doping technology, the carrier concentration is optimized, and meanwhile, the construction of a carrier transport passage in the printed film and the regulation and control of the defects are realized, so that the printed bismuth telluride film has excellent electric transport performance and thermoelectric performance in a wider temperature range. The printed bismuth telluride film is applied to thermoelectric conversion, and can realize stable output in a large temperature difference range of 273-478K.
Description
Technical Field
The invention belongs to the technical field of bismuth telluride films, and particularly relates to a printed bismuth telluride film suitable for a wide temperature range and a preparation method thereof.
Background
With the rapid development of marketization and weight reduction of devices, the development of high-performance thermoelectric thin films and devices and low-cost large-scale preparation technology are urgently required. The research on bismuth telluride-based thermoelectric thin-film materials and devices mainly focuses on high-precision preparation methods such as magnetron sputtering, thermal evaporation and molecular beam epitaxy with complex equipment operation and high cost, and the research on the traditional printing preparation technology with the advantages of low energy consumption and low cost is not mature.
The poor thermoelectric property of the printed film, especially the poor electric transport property, severely restricts the application of the screen printing thermoelectric device, which is mainly caused by the poor crystallinity and low compactness due to the thermal evaporation of the solvent and the organic matter in the printed film. In addition, researchers believe that the study of thermoelectric materials having excellent thermoelectric performance over a wide temperature range is an important condition for promoting thermoelectric power generation applications. Therefore, optimizing the electrotransport properties of printed films over a wide temperature range is of great significance and has not been reported to date.
The thermoelectric film prepared by screen printing has low performance, and the theoretical research and thermoelectric conversion application of the printed film and devices are seriously restricted. How to realize the synergistic enhancement effect of 'defect control' and 'microstructure regulation' on thermoelectric performance is the key to the development of high-performance bismuth telluride-based thermoelectric thin film materials. The technical key point is how to realize the preparation of the high-performance thermoelectric film by using a controllable printing means, and the difficulty is how to realize the filling or connection of an inner hole of the printed film and an interface so as to improve the density of the material and establish a carrier transport channel. At present, researchers adopt methods such as tellurium atmosphere sintering, high-temperature hot-pressing sintering and the like to optimize the thermoelectric performance of a printing film, but the application in a wide temperature range is difficult to realize.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a printed bismuth telluride film suitable for wide temperature range and a preparation method thereof. The method of the invention has simple operation and low cost. The bismuth telluride film prepared by the method has excellent thermoelectric performance in a wider temperature range, which greatly promotes the application of printing in thermoelectric energy conversion.
The technical scheme adopted by the invention is as follows:
a preparation method of a printed bismuth telluride film suitable for wide temperature ranges comprises the following steps:
(1) preparation of tellurium nano solder
Putting tellurium powder into a mercaptan diamine co-solution, and fully stirring until the tellurium powder is completely dissolved to form a dark purple solution; then adding a poor solvent into the dark purple solution for sedimentation, and separating out the sediment to obtain the tellurium nano solder;
(2) preparation of printing pastes
Fully and uniformly mixing functional phase bismuth telluride powder, an organic binder, a dispersant, a solvent and the tellurium nano solder in the step (1) to prepare printing slurry;
(3) substrate processing
Sequentially soaking the substrate in liquid detergent, deionized water, ethanol and acetone for ultrasonic cleaning to obtain a pretreated substrate;
(4) printing bismuth telluride film on the pretreated substrate
And printing the pretreated substrate by using the printing slurry to obtain a bismuth telluride film, and drying and sintering the bismuth telluride film in sequence to obtain the bismuth telluride film suitable for the wide temperature range.
In the step (1), the mass-to-volume ratio of the tellurium powder to the thiol diamine co-solution is 1g (6-22) mL; the mass volume ratio of the tellurium powder to the poor solvent is 1g (40-70) mL.
In the step (1), the mercaptan diamine co-solution is a mixed solution composed of mercaptan and diamine according to a volume ratio of 1 (2-10); the mercaptan is one or a mixture of more of ethanethiol, ethanedithiol, propanedithiol and butanedithiol; the diamine is ethylenediamine and/or propylenediamine;
the poor solvent is one or a mixture of more of ethanol, acetonitrile and acetone.
In the step (2), the organic binder is prepared by adopting the following method:
and (2) placing ethyl cellulose in a mixed solvent, and heating the mixed solvent under the condition of stirring to form a uniform and stable viscous solution, namely the organic binder.
The mass ratio of the ethyl cellulose to the mixed solvent is 1 (9-16).
The mixed solvent is a mixture of two or more of terpineol, butyl carbitol acetate, dibutyl phthalate and butyl carbitol;
the heating is carried out at a temperature of 70-90 ℃.
In the step (2), the dispersant is tween 80 and/or span 80; the solvent is terpineol and/or butyl carbitol acetate;
the mass ratio of the bismuth telluride powder to the organic binder to the tellurium nano solder is 8 (0.2-0.8) to 0.4-1.6; the mass ratio of the dispersing agent to the bismuth telluride powder is (0.05-0.15):8, and the mass ratio of the solvent to the bismuth telluride powder is (1.2-3): 8.
In the step (3), the liquid detergent is prepared by adopting liquid detergent and water according to the mass volume ratio of 1g (50-100) mL;
the substrate is any one of glass, quartz, polyimide, aluminum nitride and aluminum oxide.
In the step (4), the drying is slow drying, the temperature of the slow drying is 120-200 ℃, and the time of the slow drying is 30-80 min;
the sintering is carried out in an inert atmosphere, the sintering temperature is 370-470 ℃, and the sintering time is 20-60 min.
The printed bismuth telluride film prepared by the method.
The inventors and the subject group thereof found in long-term research that the printing preparation of the bismuth telluride thin film material with excellent thermoelectric performance in a wide temperature range still has great challenges. For example, in order to control the carrier concentration of a printed film and supplement the volatilization of tellurium element in the sintering process, tellurium atmosphere sintering is applied, but the method is easy to cause the uneven distribution of the components of the printed film, and the stable thermoelectric property can not be ensured in a wide temperature range. By introducing excessive tellurium powder, elements in the printed film can be relatively uniform respectively, but the intrinsic characteristic of loose and porous printed film is not improved. The film has many holes and low density, and the carrier transport is hindered. Although the density of the material is improved by high-temperature hot-pressing sintering, the saturated vapor pressure of tellurium elements at high temperature is lower, the composition segregation is larger, the defects in the printed film are difficult to regulate and control, and the preparation of the printed film with excellent thermoelectric performance is not facilitated. Further, through a large amount of experimental researches, the inventor of the application finds that the introduction of the nano solder can promote the particle bridging of the hand coating or 3D printing material at a lower temperature, improve the density of the material and optimize the thermoelectric property of the material. Finally, the printed thermoelectric thin film material with excellent thermoelectric performance in a wide temperature range is prepared by a simple and effective method.
The invention has the beneficial effects that:
the preparation method of the printed bismuth telluride film suitable for the wide temperature range comprises the steps of firstly placing tellurium powder in a co-solution of mercaptan diamine to prepare a dark purple solution, then adding a poor solvent for sedimentation to prepare a tellurium nano solder, further using the tellurium nano solder in raw materials for preparing printing slurry, finally printing the printing slurry on a pretreated substrate by using a printing technology, and drying and sintering to prepare the bismuth telluride film suitable for the wide temperature range; according to the invention, the tellurium nano solder prepared by a specific method is doped into the raw material of the printing slurry, so that the large-grain interface in the finally prepared printed bismuth telluride film is bridged, the porosity is reduced, and a carrier transport path of the printed bismuth telluride film can be effectively constructed. The electron mobility in the printed film is improved, the point defects in the film can be effectively controlled by doping the tellurium nano solder, the carrier concentration is optimized, meanwhile, the construction of a carrier transport passage in the printed film and the regulation and control of the defects are realized, the electric transport of the printed film is optimized, and the printed bismuth telluride film has excellent electric transport performance and thermoelectric performance in a wider temperature range. The printed bismuth telluride film prepared by the method is applied to thermoelectric conversion, and can realize stable output in a large temperature difference range of 273-478K.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without any creative work.
FIG. 1 is a diagram showing the electric transport properties of a printed bismuth telluride film suitable for a wide temperature range according to example 1 of the present invention;
fig. 2a is a voltammetry curve (output voltage current curve) of a thermoelectric device measured by a 105K fixed temperature difference under 273-478K for a printed bismuth telluride thin film in a wide temperature range in embodiment 1 of the present invention at different temperature ranges;
fig. 2b is an output power current curve of the thermoelectric device measured by a 105K fixed temperature difference under 273-478K for the printed bismuth telluride thin film in the wide temperature range in the embodiment 1 of the present invention at different temperature ranges;
FIG. 3 is SEM images of screen-printed films of different tellurium content nano-solders obtained in examples 1-4 and comparative example 1;
FIG. 4a is a composition analysis chart of screen-printed bismuth telluride films of different tellurium content nano solders before and after sintering;
FIG. 4b is a plot of carrier concentration and mobility for screen printed films of different tellurium content nanosolder;
FIG. 5a is a graph comparing conductivity of screen printed films of different tellurium content nanosoldings;
FIG. 5b is a graph comparing the room temperature conductivity of screen printed films with different amounts of tellurium nano-solders;
FIG. 5c is a comparison of Seebeck coefficients for screen printed films of different tellurium content nanosoldings;
FIG. 5d is a graph of power factor comparison of screen printed films of different tellurium content nanosoldings.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment provides a printed bismuth telluride film suitable for a wide temperature range, which is prepared by the following method:
(1) preparation of tellurium nano solder
Putting 1g of tellurium powder into a co-solution of 2mL of ethanethiol and 8mL of ethylenediamine, and fully stirring until the tellurium powder is completely dissolved to form a dark purple solution; then adding 40mL of acetonitrile into the dark purple solution for sedimentation, separating out a precipitate, and drying to obtain the tellurium nano solder;
(2) preparation of printing pastes
Firstly, preparing an organic binder, and specifically comprising the following steps: heating 1g of ethyl cellulose, 9g of terpineol and 2g of dibutyl phthalate to form a uniform and stable viscous solution under the stirring condition at 70 ℃, namely the organic binder;
taking 8g of functional phase bismuth telluride powder, 0.5g of organic binder, 0.1g of tween 80, 1.4g of terpineol and 1.2g of tellurium nano solder, and fully and uniformly mixing to prepare printing slurry;
(3) substrate processing
Sequentially soaking the substrate aluminum nitride in detergent water (prepared by detergent and water according to the mass-volume ratio of 1g:50 mL), deionized water, ethanol and acetone for ultrasonic cleaning, and wiping the substrate by using alcohol cotton to obtain a pretreated substrate;
(4) printing bismuth telluride film on the pretreated substrate
And (3) printing the printing paste obtained in the step (2) on the pretreated substrate by utilizing a screen printing technology to obtain a bismuth telluride film, slowly drying the bismuth telluride film at 150 ℃ for 60min, and sintering the bismuth telluride film at 400 ℃ for 30min under a nitrogen atmosphere to obtain the bismuth telluride film suitable for the wide temperature range.
Example 2
Example 2 differs from example 1 only in that: the tellurium nano solder has different doping amounts, and specifically comprises the following steps:
in the step (2), when preparing the printing paste, 8g of functional phase bismuth telluride powder, 0.5g of organic binder, 0.1g of tween 80, 1.4g of terpineol and 1.6g of the tellurium nano solder are taken and fully mixed uniformly to prepare the printing paste.
Example 3
Example 3 differs from example 1 only in that: the tellurium nano solder has different doping amounts, and specifically comprises the following steps:
in the step (2), when preparing the printing paste, 8g of functional phase bismuth telluride powder, 0.5g of organic binder, 0.1g of tween 80, 1.4g of terpineol and 0.8g of tellurium nano solder are taken and fully mixed uniformly to prepare the nano solder.
Example 4
Example 4 differs from example 1 only in that: the tellurium nano solder has different doping amounts, and specifically comprises the following steps:
in the step (2), when preparing the printing paste, 8g of functional phase bismuth telluride powder, 0.5g of organic binder, 0.1g of tween 80, 1.4g of terpineol and 0.4g of tellurium nano solder are taken and fully mixed uniformly to prepare the nano solder.
Example 5
The embodiment provides a printed bismuth telluride film suitable for a wide temperature range, which is prepared by the following method:
(1) preparation of tellurium nano solder
Putting 1g of tellurium powder into a co-solution of 2mL of ethanedithiol and 20mL of ethylenediamine, and fully stirring until the tellurium powder is completely dissolved to form a dark purple solution; adding 70mL of acetonitrile into the dark purple solution for sedimentation, separating out sediment, and drying to obtain the tellurium nano solder;
(2) preparation of printing pastes
Firstly, preparing an organic binder, and specifically comprising the following steps: heating 1g of ethyl cellulose and 9g of terpineol under stirring at 90 ℃ to form a uniform and stable viscous solution, namely the organic binder;
taking 8g of functional phase bismuth telluride powder, 0.2g of organic binder, 0.15g of tween 80, 3g of terpineol and 1.2g of tellurium nano solder, and fully and uniformly mixing to prepare printing slurry;
(3) substrate processing
Sequentially soaking substrate aluminum oxide in detergent water (prepared by detergent and water according to the mass volume ratio of 1g:100 mL), deionized water, ethanol and acetone for ultrasonic cleaning, and wiping the substrate by alcohol cotton to obtain a pretreated substrate;
(4) printing bismuth telluride film on the pretreated substrate
And printing on the pretreated substrate by utilizing a screen printing technology to obtain a bismuth telluride film, slowly drying the bismuth telluride film at 200 ℃ for 30min, and sintering at 420 ℃ for 60min under a nitrogen atmosphere to obtain the bismuth telluride film suitable for the wide temperature range.
Example 6
The embodiment provides a printed bismuth telluride film suitable for a wide temperature range, which is prepared by the following method:
(1) preparation of tellurium nano solder
Putting 1g of tellurium powder into a co-solution of 2mL of propanedithiol and 4mL of ethylenediamine, and fully stirring until the tellurium powder is completely dissolved to form a dark purple solution; adding 70mL of acetone into the dark purple solution for precipitation, separating out a precipitate, and drying to obtain the tellurium nano solder;
(2) preparation of printing pastes
Firstly, preparing an organic binder, and specifically comprising the following steps: heating 1g of ethyl cellulose, 9g of butyl carbitol acetate and 7g of butyl carbitol under stirring at 90 ℃ to form a uniform and stable viscous solution, namely the organic binder;
taking 8g of functional phase bismuth telluride powder, 0.8g of organic binder, 0.05g of span 80, 1.2g of butyl carbitol acetate and 1.6g of tellurium nano solder, and fully and uniformly mixing to prepare printing slurry;
(3) substrate processing
Sequentially soaking substrate glass in liquid detergent (the liquid detergent and the water are prepared according to the mass volume ratio of 1g:50 mL), deionized water, ethanol and acetone for ultrasonic cleaning, and wiping the substrate by using alcohol cotton to obtain a pretreated substrate;
(4) printing bismuth telluride film on the pretreated substrate
And printing on the pretreated substrate by utilizing a screen printing technology to obtain a bismuth telluride film, slowly drying the bismuth telluride film at 120 ℃ for 80min, and sintering at 470 ℃ in an inert atmosphere for 20 min to obtain the bismuth telluride film suitable for the wide temperature range.
Example 7
The embodiment provides a printed bismuth telluride film suitable for a wide temperature range, which is prepared by the following method:
(1) preparation of tellurium nano solder
Putting 1g of tellurium powder into a co-solution of 2mL of ethanedithiol and 10mL of propane diamine, and fully stirring until the tellurium powder is completely dissolved to form a dark purple solution; adding 70mL of ethanol into the dark purple solution for precipitation, separating out precipitate, and drying to obtain tellurium nano solder;
(2) preparation of printing pastes
Firstly, preparing an organic binder, and specifically comprising the following steps: heating 1g of ethyl cellulose, 10g of butyl carbitol acetate and 2g of dibutyl phthalate under stirring at 80 ℃ to form a uniform and stable viscous solution, namely the organic binder;
taking 8g of functional phase bismuth telluride powder, 0.5g of organic binder, 0.1g of tween 80, 1.4g of butyl carbitol acetate and 1.2g of tellurium nano solder, and fully and uniformly mixing to prepare printing slurry;
(3) substrate processing
Sequentially soaking quartz substrates in detergent water (prepared from detergent and water according to the mass-volume ratio of 1g:50 mL), deionized water, ethanol and acetone for ultrasonic cleaning, and wiping the substrates by using alcohol cotton to obtain pretreated substrates;
(4) printing bismuth telluride film on the pretreated substrate
And printing on the pretreated substrate by utilizing a screen printing technology to obtain a bismuth telluride film, slowly drying the bismuth telluride film at 150 ℃ for 60min, and sintering at 400 ℃ for 30min under an argon atmosphere to obtain the bismuth telluride film suitable for the wide temperature range.
Example 8
The embodiment provides a printed bismuth telluride film suitable for a wide temperature range, which is prepared by the following method:
(1) preparation of tellurium nano solder
Putting 1g of tellurium powder into a co-solution of 2mL of butanedithiol and 15mL of propane diamine, and fully stirring until the tellurium powder is completely dissolved to form a dark purple solution; adding 70mL of ethanol into the dark purple solution for precipitation, separating out the precipitate, and drying to obtain the tellurium nano solder;
(2) preparation of printing pastes
Firstly, preparing an organic binder, and specifically comprising the following steps: heating 1g of ethyl cellulose, 10g of terpineol and 1g of dibutyl phthalate to form a uniform and stable viscous solution under the stirring condition at 80 ℃, namely the organic binder;
taking 8g of functional phase bismuth telluride powder, 0.5g of organic binder, 0.1g of span 80, 2g of terpineol and 1.2g of tellurium nano solder, and fully and uniformly mixing to prepare printing slurry;
(3) substrate processing
Sequentially soaking substrate polyimide in detergent water (prepared by detergent and water according to the mass-volume ratio of 1g:50 mL), deionized water, ethanol and acetone for ultrasonic cleaning, and wiping the substrate by using alcohol cotton to obtain a pretreated substrate;
(4) printing bismuth telluride film on the pretreated substrate
And printing on the pretreated substrate by utilizing a screen printing technology to obtain a bismuth telluride film, slowly drying the bismuth telluride film at 150 ℃ for 60min, and sintering at 370 ℃ for 35 min under an inert atmosphere to obtain the bismuth telluride film suitable for the wide temperature range.
Comparative example 1
This comparative example provides a printed bismuth telluride film, differing from example 1 only in that: the preparation and doping of the tellurium nano solder are not carried out, and specifically the method comprises the following steps:
(1) preparation of printing pastes
Firstly, preparing an organic binder, and specifically comprising the following steps: heating 1g of ethyl cellulose, 9g of terpineol and 2g of dibutyl phthalate to form a uniform and stable viscous solution under the stirring condition at 70 ℃, namely the organic binder;
taking 8g of functional phase bismuth telluride powder, 0.5g of organic binder, 0.1g of tween 80 and 1.4g of terpineol, and fully and uniformly mixing to prepare printing slurry;
(2) substrate processing
Sequentially soaking the substrate aluminum nitride in detergent water (prepared by detergent and water according to the mass-volume ratio of 1g:50 mL), deionized water, ethanol and acetone for ultrasonic cleaning, and wiping the substrate by using alcohol cotton to obtain a pretreated substrate;
(3) printing bismuth telluride film on the pretreated substrate
And printing on the pretreated substrate by utilizing a screen printing technology to obtain a bismuth telluride film, slowly drying the bismuth telluride film at 150 ℃ for 60min, and sintering at 400 ℃ for 30min under a nitrogen atmosphere to obtain the bismuth telluride film.
It should be noted that the screen printing technique used in the present application can be replaced by the available printing technique, such as hand coating or direct writing method to obtain the bismuth telluride film.
Examples of the experiments
The morphology and performance of the printed bismuth telluride films obtained in examples 1 to 4 and comparative example 1 were examined as follows.
As shown in fig. 1, which is a graph of the electrical transport performance of the printed bismuth telluride film obtained in this example 1, it can be seen from the graph that the electrical conductivity and the seebeck coefficient have little change in the wide temperature range of 300-660K, which indicates that the printed bismuth telluride film has the possibility of being applied in a wide temperature range.
To further test the application assumption of the printed bismuth telluride film described in example 1 over a wide temperature range, the output characteristics of the thermoelectric device were measured over a wide temperature range (273- & ltSUB & gt 478- & gt) at a fixed temperature difference of 105K (FIGS. 2a & 2 b). As can be seen in fig. 2a, the voltammogram exhibits 4 nearly parallel lines and a more stable maximum open circuit voltage is obtained: 11.13mV (378K), 11.34mV (408K), 11.57mV (438K) and 11.76mV (478K). It can be seen in fig. 2b that the maximum output powers are 24.5, 27.1, 27.0 and 27.7 muw respectively, indicating that a relatively constant output power can be generated over a wide temperature range.
SEM images of screen-printed bismuth telluride films of different tellurium nano solders prepared by the methods described in example 1 (tellurium nano solder content of 12 wt.%), example 2 (tellurium nano solder content of 16 wt.%), example 3 (tellurium nano solder content of 8 wt.%), example 4 (tellurium nano solder content of 4 wt.%) and comparative example 1 (tellurium nano solder content of 0 wt.%) in the order shown by d1-d2, e1-e2, c1-c2, b1-b2, a1-a2 in FIG. 3, respectively, as can be seen from the drawings: bi in the film without tellurium nano solder (FIG. 3a1-a2)2Te3Only a slight sintering of the particles takes place and the film has the smallest particle size and a larger porosity. With the increase of the addition amount of the Te nano solder, the micro-morphology of the film is obviously changed, the particle size is increased, and the porosity is reduced.
FIG. 4a shows the composition analysis chart before and after sintering of screen-printed bismuth telluride films of different tellurium content nano-solders prepared by the method described in examples 1-4 and comparative example 1, and it can be seen from the chart that: with the increase of the addition amount of the tellurium nano solder, the content of tellurium in the unsintered film is increased. Due to the higher saturated vapor pressure of tellurium, the tellurium content of the sintered film is significantly reduced, which will lead to a change in internal defects of the film.
FIG. 4b shows the carrier concentration and mobility of screen-printed bismuth telluride thin films with different tellurium content nano-solders prepared by the methods described in examples 1-4 and comparative example 1The shift rate graph can show that: the film without the tellurium nano solder shows p-type carrier conduction, and the carrier concentration and the mobility are lower; along with the increase of tellurium nano solder, the carrier concentration is increased, and the mobility is obviously improved. The concrete explanation is as follows: tellurium vacancy generation by tellurium evaporation during sintering of bismuth telluride thin film
More bismuth inversion defects are generated
And cation vacancies
And inhibit tellurium inversion defects
Is generated. Generated inversion defect
And cation vacancies
Exhibits acceptor behavior, thus increasing the concentration of holes. Accordingly, the film without the nano solder added shows the behavior of p-type conduction. With the increase of the tellurium nano-solder,
the concentration of (3) is reduced and the acceptor behavior is suppressed. That is to say that the position of the first electrode,
is reduced to generate more
And is suppressed of Bi'TeExhibits an acceptor effect. Accordingly, the carrier concentration gradually increases with the increase of the tellurium nano-solder. While the printing sheetThe increase of film mobility with increasing tellurium nanosolder content is mainly due to the construction of the carrier transport path.
Fig. 5a shows a graph of conductivity comparison of screen printed bismuth telluride films of different tellurium content nano-solders prepared by the methods described in examples 1-4 and comparative example 1, from which it can be seen that: along with the increase of the testing temperature, the conductivity of the Te-free nano solder sample is obviously increased, and due to the bipolar conduction generated by thermal excitation, Bi is enabled to be in2Te3The electrons and holes in (1) participate in the conduction at the same time. This trend gradually decreases with increasing Te nanosolder content, with samples with a content of 12 wt.%, in particular 16 wt.%, showing a substantially decreasing trend with increasing temperature. It is demonstrated that the introduction of the Te nano-solder is advantageous for reducing the bipolar conduction. Due to the change of intrinsic point defects due to the evaporation of Te during sintering, p-type conductivity occurs in the thin film without Te nano-solder, while n-type conductivity occurs in the thin film with Te nano-solder.
As shown in fig. 5b, which is a graph comparing the room temperature conductivity of screen-printed bismuth telluride films with different tellurium content nano-solders prepared by the methods described in examples 1-4 and comparative example 1, it can be seen that: as the Te nanosolder content increased, the room temperature conductivity of the printed film exhibited increasing and then decreasing room temperature conductivity. The electron path construction and the point defect engineering regulate and control the carrier mobility and the carrier concentration, and the conductivity of the film is improved.
As shown in fig. 5c, which is a comparison graph of seebeck coefficients of screen-printed bismuth telluride films with different tellurium content nano solders prepared by the methods described in examples 1-4 and comparative example 1, it can be seen that: the change rule of the Seebeck coefficient of the film along with the test temperature also proves that the introduction of the Te nano solder is beneficial to reducing the bipolar conduction through defect engineering. With the increase of the content of Te nano solder, the temperature of the peak Seebeck coefficient is delayed, most current carriers are rapidly increased, the Fermi level is gradually reduced from the edge of a valence band, intrinsic excitation and bipolar conduction at high temperature are inhibited, and the application in a wide temperature range is facilitated.
As shown in fig. 5d is trueThe power factor comparison graphs of the screen-printed bismuth telluride films with different tellurium content nano solders prepared by the methods described in examples 1-4 and comparative example 1 show that: the power factor of the film containing the nano solder is obviously superior to that of the film containing no solder; the power factor of the solder film containing 12 wt.% is optimal; the power factor is stable in the large range of 300-500K; at 395K, a maximum of 4.65W cm was reached-1K-2。
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a printed bismuth telluride film suitable for wide temperature ranges is characterized by comprising the following steps:
(1) preparation of tellurium nano solder
Putting tellurium powder into a mercaptan diamine co-solution, and fully stirring until the tellurium powder is completely dissolved to form a dark purple solution; then adding a poor solvent into the dark purple solution for sedimentation, and separating out the sediment to obtain the tellurium nano solder;
(2) preparation of printing pastes
Fully and uniformly mixing functional phase bismuth telluride powder, an organic binder, a dispersant, a solvent and the tellurium nano solder in the step (1) to prepare printing slurry;
(3) substrate processing
Sequentially soaking the substrate in detergent water, deionized water, ethanol and acetone for ultrasonic cleaning, and wiping the substrate by using alcohol cotton to obtain a pretreated substrate;
(4) printing bismuth telluride film on the pretreated substrate
And printing the pretreated substrate by using the printing slurry to obtain a bismuth telluride film, and drying and sintering the bismuth telluride film in sequence to obtain the bismuth telluride film suitable for the wide temperature range.
2. The preparation method of the printed bismuth telluride film according to claim 1, wherein in the step (1), the mass-to-volume ratio of the tellurium powder to the thiol diamine co-solution is 1g (6-22) mL; the mass volume ratio of the tellurium powder to the poor solvent is 1g (40-70) mL.
3. The method for preparing the printed bismuth telluride film according to claim 1, wherein in the step (1), the thiol diamine co-solution is a mixed solution of thiol and diamine according to a volume ratio of 1 (2-10); the mercaptan is one or a mixture of more of ethanethiol, ethanedithiol, propanedithiol and butanedithiol; the diamine is ethylenediamine and/or propylenediamine;
the poor solvent is one or a mixture of more of ethanol, acetonitrile and acetone.
4. The method for preparing a printed bismuth telluride film according to claim 1, wherein in the step (2), the organic binder is prepared by the following method:
and (2) placing ethyl cellulose in a mixed solvent, and heating the mixed solvent under the condition of stirring to form a uniform and stable viscous solution, namely the organic binder.
5. The method for preparing the printed bismuth telluride film according to claim 4, wherein the mass ratio of the ethyl cellulose to the mixed solvent is 1 (9-16).
6. The method for preparing a printed bismuth telluride film according to claim 4 wherein the mixed solvent is a mixture of two or more of terpineol, butyl carbitol acetate, dibutyl phthalate and butyl carbitol;
the heating is carried out at a temperature of 70-90 ℃.
7. The method for preparing a printed bismuth telluride film according to claim 1, wherein in the step (2), the dispersant is tween 80 and/or span 80; the solvent is terpineol and/or butyl carbitol acetate;
the mass ratio of the bismuth telluride powder to the organic binder to the tellurium nano solder is 8 (0.2-0.8) to (0.4-1.6); the mass ratio of the dispersing agent to the bismuth telluride powder is (0.05-0.15):8, and the mass ratio of the solvent to the bismuth telluride powder is (1.2-3): 8.
8. The preparation method of the printed bismuth telluride film according to claim 1, wherein in the step (3), the liquid detergent is prepared from liquid detergent and water according to a mass-volume ratio of 1g (50-100) mL;
the substrate is any one of glass, quartz, polyimide, aluminum nitride and aluminum oxide.
9. The method for preparing a printed bismuth telluride film as defined in claim 1, wherein in the step (4), the drying is slow drying at a temperature of 120 ℃ to 200 ℃ for 30-80 min;
the sintering is carried out in an inert atmosphere, the sintering temperature is 370-470 ℃, and the sintering time is 20-60 min.
10. A printed bismuth telluride film produced by the method as claimed in any one of claims 1 to 9.
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| CN114249305A (en) * | 2020-09-23 | 2022-03-29 | 北京信息科技大学 | Bismuth telluride-based thermoelectric film with stable wide-temperature-range performance and preparation method thereof |
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